High-speed silver dye bleachout taking and printing film



Patented Apr. 21, 1953 HIGH-SPEED SILVER DYE BLEACHOUT TAKING AND PRINTING FILM Joseph A. Sprung, Easton, Pa., assignor to General Aniline & Film Corporation, New York, N. Y., a corporation of Delaware No Drawing. Application April 18,1950,

Serial No. 156,730

12 Claims. (01. 95-6) The present invention pertains to high speed multilayer material for processing by the silver dye bleachout method, which may be used either for taking or printing material, and which is characterized by the presence in the layer destined to yield the cyan image, of a color former reactive with a metal salt to form a cyan metal complex compound.

The most popular commercial multilayer color material available at the present time is processed by the method known as color development. The dye images formed in such material by this mode of processing are of the azomethine or quinonimine class.

During the color development process, the exposed silver halide functions as an oxidizing agent of the color developer which in turn combines with the color former either present in the multilayer material or in the color developers for the same to yield yellow, magenta and cyan azomethine or quinonimine dye images in the blue, green and red sensitive layers respectively.

Dyes of the azomethine or quinonimine class have a number of shortcomings, the principal one being their instability toward light and atence of an azo dye coupling component with a sulfonhydrazide. During development the sulfonhydrazide is converted to a diazo sulfone and reacts directly with the coupling components to form azo dyestuffs.

Another and rather widely discussed method involving the formation of azo dye images is the silver dye bleachout process. This method operates on the principle that yellow, magenta and cyan azo dyestuffs which are either incorporated in or subsequently formed in the blue, green and, red sensitive layers of a multilayer material are bleached selectively in situ with a previously developed silver image. In this case the silver image functions as a reducing agent and the results are essentially the same as those produced by the color development method in which the silver halide is the imagewise oxidant.

The silver azo dye bleachout material which is commercially available at the present time contains the azo dyes in the sensitized layers 2 thereof. The azo dyes are rendered non-migratory in such layers by precipitation therein by means of biguanides. Such material from its very nature is of slow speed. This is attributable, on the one hand, to the absorption of light by the azo dyes present in the layers which act as filter dyes, and, on the other hand, to the strong desensitizing action of the biguanides. For this reason. the silver azo dye bleachout procedure has been limited in application to the processing of printing material.

I have now discovered multilayer material capable of being processed by the silver dye bleachout method which is free from the objections to the presently available bleachout material. My multilayer material, because of its inherent speed, is capable of being utilized either for taking material, i. e., for exposures in the cameras, or as printing material.

My multilayer taking material is characterized by the presence in the emulsion layers designed to receive the yellow and magenta images of colorless non-diffusing azo dye couplers capable of reacting with one and the same diazonium salt to form yellow and magenta dyes. The layer de-.- signed to receive the cyan image contains a colorless heterocyclic nitrogenous compound which is capable of being bleached by a silver dye bleaching bath and which has the ability to react with a metal salt to form a cyan metal complex.

This material permits the formation of the yellow and magenta azo dyes and the cyan metal complex at a point subsequent to exposure so that the material has high initial speed.

My multilayer material utilized as printing material is characterized by the presence in the layers designed to receive the yellow and magenta images of yellow and magenta non-diffusing azo dyes which are bleached. by the usual silver dye bleachout baths. The layer designed to receive the cyan image, however, contains the colorless heterocyclic nitrogenous compound capable of forming a cyan metal complex upon treatment vith a metal salt.

Taking and printing material of the type mentioned, the processing of such material by the silver dye bleachout method, and a silver halide emulsion designed to receive the cyan dye image and containing a colorless heterocyclic nitrogenous compound capable of being bleached by a silver'dye bleachout bath and of forming a cyan metal complex compound upon reaction with a metal salt constitute the purposes and objects of the present invention.

It is apparent from what has been said that the key to my invention is the utilization in the red sensitive layer of multilayer material of the colorless heterocyclic nitrogenous compound which is capable of yielding cyan metal complexes upon treatment with a metal salt. It is the correlation of the function of the layer containing such compound with the layers containing the colorless azo dye couplers for the yellow and magenta azo dyes in the silver dye bleachout method which leads to the improvements wrought by my invention.

It is known that there are color couplers which by reaction with one and the same diazonium salt will yield yellow and magenta azo dyestuffs. It has not been possible, however, to find a coupler which will react with such diazonium salt to simultaneously form a cyan azo dye. It is therefore necessary to utilize for the formation of the cyan dye image a compound which is sensitive to the silver dye bleach bath and which is likewise capable of forming a cyan color by reaction with an agency other than a diazonium salt solution.

It has been ascertained that compounds which will effectively produce cyan colors of the desired density must meet a number of prerequisites, particularly the following:

('1) The compound must not desensitize photographic emulsions;

(2) The compound must be capable of being rendered non-migratory in photographic emulsions by permitting the addition of a non-diffusing radical thereto.

(3) The compound must be readily bleached in situ with the silver image.

(4) The compound must produce a cyan metallic complex which has acceptable minus-red spectral characteristics.

*(5) The compound must form the cyan complex easily and such complex must not be fugitive to atmospheric conditions and must be stable to gelatin at its isoelectric point.

A great many components have been tested for the purpose of ascertaining their value as couplers for formation of the cyan complex dye. My conclusion based upon such extensive work is that the compounds which meet the aforementioned prerequisites are those heterocyclic compounds which contain the following poly-functional group either as such or in the indicated tautomeric forms: 2-isonitroso-1,3-diketone,

The heterocyclic compounds possessing such polyfunctional groups have the following constitution:

Y is hydrogen, an aliphatic radical such as alkyl, i. e., methyl, ethyl, propyl, amyl, decyl, dodecyl,

tetradecyl or the like, carboxyalkyl, carboxy methyl, carboxy ethyl and the like, sulfoalkyl, i. e., sulfomethyl, sulfoethyl, alkyl-sulfonyl such as methyl sulfonyl, ethyl sulfonyl and the like, an aromatic radical such as aryl, i. e., phenyl, naphthyl and the like, alkoxy aryl such as methoxy phenyl, ethoxy phenyl, tetradecoxy phenyl and the like, aryl sulfonyl, such as phenyl sulfonyl, aminophenyl sulfonyl and the like, sulfoaryl, such as sulfophenyl and the like, or cyano, R and R are hydrogen, alkyl as above, or aryl as above, and Z is =0 or =NH.

The above compounds may exist in the form indicated or in the following tautomeric forms:

The following compounds illustrative of those within the above classification have been found to be suitable for my purposes:

5-nitrosobarbituric acid or [5-uitroso-2,4=,6-trihydroxypyrimidine] HO I OH NO 2-amino-4,6-dihydroxy-5-nitroso-pyrimidine H N mNVo H N 0 6-amino-2,6-dihydroxy-5-nitroso-pyrimidine mNM-on N 2,6-diamino-4-hydroxy-5-nitroso-pyrimidine 5. NH

il II NOH 1,3-diethylvioluric acid or [1,3-diethyl-S-oximino-hexahydropyrimidine-trione-2,4,6]

23. 2 (4- aminophenylsulfonamido) ,6-dihy-' droxy-5-nitrosopyrimidine. 24. x Y

NOH- 1-pheny1-2-pheny1imino-5-isonitrosohexahydropyrimidine- (Hone-4,6

N O H Z-cyanimin0-1-phenyl-5-isonitrosohexahydropyrimidinedi0ne- 6 HOVOH 3 2-'dib11tyl.mii1o-4,Gfiihydroxy-Er-nitrosopyrimidine 27.. 2-di0ctylamino 41,6 dihydroxy-S-nitrosopyrimidine.

HOV-NH: .No

6-amino-2-cyanamino-4-hydroxy-5-nitrosopyrimldine 29. Ha

Roxie,

N0. 6-amino-2-(-aminophenyhsulfonamido)-4-hydroxy-5- nitrosopyrimidine H27C k NCH2CH2SO1H V SO | 1 NO N-( 6-amino-4-hydroxy-5-nitroso2pyrimidyl ).-N-o etadecyltaurine H379 m- C H10 Has 0 3E N0 6-nitroso-2-phenyl-5,7-(llhydrxy-l,3,4-triazaindolizine All of the abov e 'compounds have the ability of forming color complex metal salts by reaction with soluble metal salts. They are particularly characterized by "their ability to yield 'blu'e green colors by reaction with water soluble compounds containing ferrous iron, such as ferrous chloride, ferrous sulfate, ferrous ammonium sulfate, and the like.

The above compounds can-be synthesized according to the followingstandard procedures:

(1) Condensation of a urea, thiourea, or guanidine, derivative with .ethylisonitroso malonate, or ethyl isonitrosocyanoacetate as follows? cyanoacetate, followed by nitrosation of the product as follows. I

In these equations, R li angl X have the values given above.

My printing material is a tripack, the three layers of which are sensitized according to conventional practice, i. e., the outermost layer to blue light, the intermediate layer to greenlight, and

end iix di i th ,subieeted-v a solution hic is capable 9f 7 9 the lowermost layer to red light. The blue sensitive layer contains a non-difiusing yellow azo dyestuff in which the nondiffusing group appears in the diazo component. The coupling component for such dyes is preferably a pyrazolone. Suitable dyes and their method of manufacture are described. in my cepending appl catio aer No 3, 55 filed August 1-1, 1%3- The g eense .sitive layer contains a nensdii usine magenta azo d e in which t e nomdifiusin group ape pears the diazo component. The coupling component is preferably a naphthql. .Satisfactory dyes and their method of preparation are disclosed in the aforesaid application Serial No. 43,756. The red sensitive layer contains one of the aforesaid heterocyclic nitrogenous compounds. said c m ound Prefe ably eerlteis ne radi a rendering the ompound test t diftus eii the e s on a er- ,Sueh material Prc e sed teaser-dies t the bleaeheu hod as e l ws; The ma e ble h ng ba h o th t e d sented 2 3 my pendi g pp c t o S ri l ,NQ- 71 322 fi e Peeember 1946, new Ret s 5. This hath d t eys t .d esat .r re and modifies the heterocyclic nitrogenous com,- pound in the red sensitive layer so that it is no longer capable of forming 'a cyan metal comlayer located a non-,difiusing azo magenta color f er, ab y a aphth li Th e ;.s

tive layer contains one of ,the at cyclicnitrogenous cyan complex M t W v has b n ed iast d fiusi n' the slon.

akin film is p essed foll ws; t is xp d, e op d in a black and W. developer, and fixed. It is then treated with ,a diazowith the color formers in the blue an n sensitive layers to produce therein yellow magenta azo dyes respectively. Eref erably the diaz n um com ou i one re ulti e x m the tetrazotization of ,a sulfonated beng dine uch -be 2. ii 1fen e eeid- Th ri ek is hen treate with a s lve d e leee b o t e purnese Q .des reyine. the re dyes a t e s l e image and 0 b eachin the cyan om ex farmer a the si v rim ee.

' si maseis the b eaehedend t esilve -helides remaining removed by fixing. Atthi l0 EAMPLE i a mo-watercress-,5:came ew midiae are a solution of 1.15 parts of so i m :25 parts of absolute alcohol, there was added Mk5 parts of ethyl isonitrosomalonate, 2.25 parts of eid carbonat and parts .9; abse ut 1- cohol. The reaction mixture was stirred vigsir undei ifeilus for th ee Ih brie e rem ved by iilt ei washed w th Le a laedetrie an in eh weight was ma eria dissolved .i so is Qt wa er was ac dified wi e e 9imes wa s eetesi e e filter washes with wa er .ei ed- Elie yie d was .2. EXAMBLEQ 2 cyanoamino 4,6 ding dreary 5 mtmsopyrimidine This product prepared according to the method of Example 1, while substituting for e ee siine arbeneie. an e uiva ent aiiastiiy of hri am de- Er e 2 .decylamz'no 4,6 dii ydrowy 5 nitric.- sopyrimidine T a .selu i ii o a Pa :ei adism 9f e elute alcoh th re wa ad ed .24 'P. is of ethyl malenate and 23 Part at l yl uand ne alrh Pre ared 911 lfi lfiilm 3. .1 5 e axiemidel and't e Whole was refluxed. hours. After the mixture beenconcentrated by .ereperat on, it diluted w th .199 Parts of Weter- Aeisi i eet ea w th aceti a id was s ted part f 2-deeriemin a .firsiiii snee' mrimid ne 1 part of the above product was dissglyed in 25 parts of absolute alcohol, with the aid of 10% sodium hydroxide solution. A solution of .35 part of sodium nitrite in -5 parts :of water was added, and the whole'was slowly acidified with 6N HCl to a HQI 2. Aite tlieedd ie 9.1. .1510 Parts of Wat r. the .lireeil tetesl s1 retained by filtrationemi wa Washed w th water.- trosation procedure was repeated twice. yield of air-dried product was .9 part.

.zecctlzeeymetl yl mmwefi-disasterscitiosqgyrimieiine To parts of amyl alcohol there was added 4375 parts ofethyl isonitrosomalonate, 2.9 parts of guanidinoacetic aoidand 2.? :peirtepf so methoxide. The mixture .was .flliiieti W hours. The pink solid WaS:;Qo.11 -1 .931. ,iE-ill'ei... washed with ethanol and air dried. The weight was 1.8 parts.

E AM LE 6 2 (2 -tec-adeco-my=5'esiilfeamzmo) -4,6dihydromy- 5 mitrosopyrimidine a. warmer:coxm nangnouamptyn e- SULEONIQ ,AQZQQ xinhitu e at .131 per se ewte a e cs netane ilic acid, 0.21 part of cyanamide and i-0 ple 3.

1 l of normal butyl alcohol was refluxed for 22 hours. The reaction mixture was cooled, and the solid material was removed by filtration. The filter cake was extracted three times with boiling ethanol, leaving 1.5 parts of the guanidine derivative.

B. CONDENSATION WITH MALONIC ESTER To a solution of 0.32 part of sodium in 10 parts of N-butyl alcohol, there was added 0.64 part of ethyl malonate, 1.5 parts of 2-tetradecoxyphenylguanidine-5-sulfonic acid and 18 parts of butyl alcohol. The whole was refluxed for 15 hours. After the mixture had been cooled, the yellow solid was removed by filtration and was washed with ethyl alcohol. A sample of the material was nitrosated according to the procedure of Exam- EXAMPLE 7 4,6f-dihydrozry-2-phenyZsuZfonamido-5- nitrosopyrzmidine A solution of 2.3 parts of sodium in 50 parts of absolute alcohol was treated with 9.5 parts of ethyl isonitrosomalonate which had been dissolved in 50 parts of absolute alcohol, and parts of benzenesulfonylguanidine (prepared by benzenesulfonyl chloride and guanidine carbonate). The whole was refluxed for 3 hours. The pink colored precipitate was removed by filtration, suspended in water and acidified with HCl.

The yellow colored precipitate was removed by filtration, and was recrystallized from water. The yield was 3.5 parts.

4,6 dihydroxy-2-ethylsulfonamido-5-n.itroso pyrimidine is prepared as above excepting that there is used in lieu of the benzene sulfonyl guanidine an equivalent quantity of ethyl sulfonyl guanidine. 7

EXAMPLE 8 2 (4-aminophenylsulfonamido) -4,6-dihydrory-E-nitrosopyrimidine This product is prepared by the method of Example 7, While substituting for the phenyl sulfonylguanidine, an equal quantity of suliaguanidine.

EXAMPLE 9 1-phenyl-2-phenylimino-5-isonitrosohexahydropyrimidine-dione-eifi This product is prepared according to the method of Example 7, while substituting for the phenylsulfonylguanidine, an equal quantity of N ,N-diphenylguanidine.

EXAMPLE 1O Z-cyaniminO-I -phenyl-5-isonitrosoheardhydropyrimidine-dime-4,6

This product is prepared according to the method of Example 7, while substituting for phenyl sulfonylguanidine, an equal quantity of phenyldicyandiamide.

EXAMPLE 11 2-dibutylamino-4,6-dihydro:cy-5-nitrosopyrimidine This product is prepared according to the method of Example 6, while substituting for 2- tetradecoxy-phenylguanidine-5-sulfonic acid, an equivalent quantity of N,N-dibutyl guamdine (prepared from dibutylamine and S-methylisothiouronium sulfate).

EXAMPLE 12 2-dioctyla.mino-4,6-dihydroa:y-S-nitrosopyrimidine This product is prepared according to the method of Example 6, while substituting for the 2-tetradecoxy-phenylguanidine-5-sulfonic acid, an equivalent amount of N,N-dioctylguanidine (prepared from dioctylamine and S-methylisothiouronium iodide).

EXAMPLE 13 6-amino-Z-cyanamino-4-hydrory-5-nitrosopyrimidine To a solution of 1.84 parts of sodium in 30 parts of absolute alcohol, there was added 1.7 parts of dicyandiamide, 2.84 parts of ethyl isonitrosocyanoacetate and '70 parts of absolute alcohol. The whole was refluxed with stirring for 48 hours.

The precipitate was removed by filtration and was washed with ethanol. The sodium salt was dissolved in water, and the resulting solution was acidified with HCl to a pH of 1. The yellow pyrimidine derivative was removed by filtration,

washed with water and dried. The yield was 3.5 parts,

EXAMPLE 14 6-amino-2- (4-aminophenylsulfonamido) -4- hydrody-5-nitrosopyrimidine This product was prepared according to the method of Example 13, substituting for the dicyandiamide an equivalent quantity of sulfaguanidine.

EXAMPLE 15 N- (ti-amino-4-hydrozcy-5-nitroso-2-pyrimidyl) -N-octadecyltaurine (a) N-OCTADECYL'IAURINE A mixture of 20.5 parts of octadecylamine and 10.6 parts of sodium-2-bromoethanesulfonate was stirred at PTO- C. for 12 hours. The reaction mixture was allowed to cool to room temperature, broken up into small lumps and extracted with acetone in a Soxhlet apparatus until the unchanged octadecylamine was removed. (About 3 to 5 hours were required). The nearly white, insoluble material Weighed 18 parts after drying The solid was ground to a fine powder and was suspended in 275 parts of warm water. The addition of 25 [parts of 20% sodium hydroxide solution gave a clear viscous solution. This was filtered by suction, and the clear filtrate was acidified with G-N-sulfuric acid. After the mixture had been cooled to 10 C., the precipitate was removed by filtration and was washed with cold water, Recrystallization of the moist filter cake from dilute ethanol, using bone black for decolorization, yielded 8 parts of N-octadecyltaurine. The product does not have a sharp melting point but liquefies at about 290 C. in a preheated bath.

(1)) N-GUAN YL-N-O CTADECYLTAURINE f To a refluxing solution of 11.5 parts of N- octadecyltaurine in 20 parts of butyl alcohol, there was added dropwise during a period of 5 hours a solution of 4 parts of cyanamide in 10 parts of butyl alcohol. After the addition was complete, the reaction mixture was refluxed for an additional 10 hours. A thick crystalline mass was produced in the cooled mixture. This was diluted with an equal volume of ethyl ether and (c) ETHYL ISONITROSOCYANOACETATE To a well-agitated cooled solution of 75 parts of sodium nitrite in 390 parts of water, there was added 102 parts of ethyl cyanoacetate and the 1 whole was treated with 75 parts of glacial acetic acid. The solution turned yellow and, after /2 hour, a yellow solid began to separate. After the mixture had been allowed to remain in an ice bath for two hours, the isonitroso compound was removed by filtration. The solid became colorless when it was digested with 150-parts of water containing 7 parts of HCl. The compound was dissolved in ether, the supernatant liquid was extracted with ether, and the combined ether solution was dried overfDrierite. After the solvent had been removed, the residual isonitroso derivative was crystallized from water. The yield was 66 parts, melting at 128C. i

(d) N- (4HYDROXY-5-NITROS0-6AMINO-2-PYRIDYL) N-OCTADECYLTAURINE (DISODIUM SALT) To a well-agitated refluxing solution of 8.1 parts of sodium in 550 parts of absolute ethanol, there was added 42 parts of N-guanyl-N-octadecyltaurine, followed by 13.5 parts of ethyl isonitrosocyanoacetate. The mixture first appeared yellow, gradually turned orange, finally, after 8 hours, became a deep red color. After a reflux period of 48 hours, the solid pyrimidine derivative was removed by filtration, washed with hot absolute ethanol and air dried. The product was purified (removal of unchanged N-gaunyl-N-octadecyltaurine) by a Soxhlet extraction with absolute ethanol. The yield was 51.7 parts.

EXAMPLE 16 N- (4,6-dihydromy-5-nitroso-2-pyrimidz Z) N-octadecyltaurine (a) ETHYLISONITROSOMALONATE.

To a stirred mixture of 160 parts of ethyl malonate and 180 parts of glacial. acetic acid, there was added dropwise during a period of 9 hours a solution of 190 parts of sodium nitrite in 225 parts of water. The temperature was kept at 20-25 C; After the mixture had been allowed to remain overnight, the organic layer was separated and was diluted with twice its volume of ether (about 500 parts was required). The ether solution was washed in a separatory funnel with 1700 parts of 1% sodium carbonate solution, in 5 portions, to neutralize the acid. At the end of the last extraction, the wash water showed a pH of 7 and wa pale yellow in color. The ether'solution was washed further with 3 portions of water. Afterthe solution had been dried over Drierite, the ether was removed and the residue was subjected to a vacuum, distillation. The distillate, boiling at 149 C./2.5 mm. was a viscous colorless liquid which was obtained in a yield of 117 parts.

(1)) N-(4,6-DIHYDR0XY-2-PYRIMIDYL)FN- OCTADECYLTAURINE To a solution of .7 .part of sodium in 20 parts of absolute alcohol, there was added asolution of 1.8 parts of ethyl malonate and 4.2 parts of N- .14 guanyl-N-octadecyltaurine in 15 parts of absolute ethanol. The solution was heated under reflux for a period of 5 hours. The reaction mixture was concentrated to a thick paste on the steam bath, cooled, diluted with ether and removed by filtration. The trisodium salt was dissolved in 25 parts of water and was precipitated from the solution by the addition of 6N sulfonic acid. The product which was removed by filtration, washed with water and air dried, was obtained in a yield of 3 parts.

( c) N (4,6-DIHYDROXY-5-NITROSO-Z-PYRIMIDYL) N-OCTADECYLTAURINE A solution of 3 parts of N-( lfi-dihydroxy-Z- pyrimidyl) -N-octadecy1taurine in 50 parts' of hot ethanol was made acid to Congo Red with I-ICl, and was cooled in an ice bath to 10 C. A 10% aqueous solution of sodium nitrite was added until a positive test was obtained on starch-iodide paper. After the excess nitrous acid had been destroyed with suliamic acid, the pale orange precipitate was removed by filtration and was washed with cold ethanol. The wet solid was suspended in 50 parts of ethanol, acidified with HCl and was again treated with 10% aqueous sodium nitrite solution until a positive test with starch iodide paper was obtained. The product was removed by filtration and was washed with cold ethanol and with ether. The yield was 2.7 parts. After recrystallization from ethanol, 1.2 parts of the purified pyrimidine derivative was obtained.

SYNTHESIS OF COLOR FORMERS EXAMPLE 17 A20 yellow color former 1 (3 stearamidophenyl) 5 oxo 2 pyrazoline-3-carboxylic acid.

NH0 0 CnHa A well-agitated warm (steam bath) solution of 53.7 parts of I-(B-aminophenyl) -5-oxo-2l-pyrazoline-S-carboxylic acid in 11 1 parts of pyridine and 336 parts of dimethylformamide was treated with 89 parts of freshly prepared stearoylchloride over a period of 1% hours. The solution was heated on a steam bath until the diazotization test for free amino group was negative. The reaction mixture was poured into a solution of 128 parts of concentrated HCl in 2000 parts of water, and the precipitate was removed by filtration and was washed with water. After the compound had been dried in an oven at 50 C., it was extracted in a Soxhlet apparatus with high boiling petroleum ether to remove the stearic acid. The extracted solid was dissolved in a minimum amount of boiling pyridine, decolorized with Norite, and was treated with hot glacial acetic acid (approximately three times the volume of pyridine) to incipient cloudiness. Th precipitated color former, which was removed by filtration from the cooled (50 C.) solution, was washed with cold ethanol and air dried. The yield was 75.5 parts.

EXAMPLE 18 for green a noh-diffusing magenta azo dye. fillfil'l A20 magenta color former as 8 (3 stearamiclobenzamido) 1 naphthol- 3,6-disu1fonio acid NH OH it I N HO O .CnHss N=HN f moss, soma- .zl'll ii NHGQGHEN 0H NE. m l 01" H038 SO3H To a solution of 92 parts of finely powdered o- (,3 amino'benaamido) 1 naphthol 3,6-di- W O S suifonic acid in 400 parts of dimethylformamide 3* I nd 100 parts of pyridine there was slowly added (Seems, momma U .S p1iq3t19nerilN0.3,158)

61 parts of freshly prepared stearoyl chloride. p The mixture was heated on a steam bath for (6) el m Separation e minutes and then additional stearoyl chloride 4 W) Reg-Sensitive 1aye? P e b d per es was added until a diazotization test showed the age'latmosflver halide emulsien ns z amino group to be completely acylated. The m 3 non-diffusing Cyan pone l h [a reaction mixture was poured into 2000 parts of 05 OH 15% sodium chloride solutionand 100 parts. of concentrated HCl. After a period of 15 minutes, HOSMCHFCHK the precipitate was removed by filtration, dl- N---.0 o No ,gest'ed withzooo parts of 15% sodium chloride solution and-was again removed by filtration. Q0 I The filter cake was dried in vacuoatfii) C. The or 0H dried finely powdered solid was extracted once OH with boiling acetone and twice. with low boiling petroleum ether. Sodium chloride was elim- Q- inated by an extraction of the product with N-C c o dimethylformamide. The solvent was removed 11 \N=C/ by vacuum distillation and the residue, whioh was digested with acetone, weighed 109.5 parts. NHI

v ExsmrmziZO PREPARATION OF MULTILAYER PRINTING MATERIAL 40 Processing of multilayer printing material EXAMPLE 19 1.--Exp0sure. Step 2 .-Development of primary silver image (1) Blue sensitive layer prepared by dlspersmg for '7 minutes t a developer t t t a 1.. in a gelatino-silver halide emulsion a non-difiuslows; ineyellow .azo dye such as:

30,1 1 at C0.. .750 ,Metol i 2 '15 2N Sodiumsulfite anhyd.) g; 45.0 oimooo 03:11 N l sodium bisulfite t ;g 1.0 Ha NHCDCnHu Hydmqumone 3- Sodium carbonate monohyd ;g 6.0 Potassium bromide -g- 0.8 Water to make c 1000 803M Stein 3.-Shortstop and fix'for' 5 minutes with:

or Part 1.

some Water Y Y. cc 500 Sodium thiosulfate 'g 240 G iHiO OC-(J--C''-N=N- Part 2:

N OH

K' Water Sodium .sulfite anhyd -e- -g--. 15 5 5 Acetic acid v(2 8' 7b s. 'cc 15 Potassium alum i i- 15 Add Part 2 to Part Land add water to make v i I V c 1000 cc. I V ea sis =f-* St 4. w shfor-5mmuta Step 5.-.-Harden for .5 minutes with 122) Gelatin separation layer. 1 I .3) Filter layer of yellow colloidal silver. Water cc 1000 (4) Gelatin separation layer. Formaldehyde 6%).iae-.. .l ..ico I (5) Greensensitive layer-preparedby dispers- Sodium bicarbonate g; 50 me, in. a, gelatino silver halide emulsion sensitized,, Stand-Washfor 3 minutes.

17 r Step 7.-Imagewise reduction of color components for 10 to 20 minutes with:

Water cc 1000 Sulfuric acid (1.84) cc 75 Potassium iodide g 10 Sodium hypophosphite g Quinoline g 50 Step 8.Wash for 5 minutes. Step 9.Remove residual silver image by treatment for 5 minutes with:

Water cc 1000 Copper sulfate ..g 100 Potassium bromide g 100 Hydrochloric acid cc 5 Step 10.--Wash for 5 minutes. Step 11 .--Fix residual silver halide for 5 to minutes with:

Water oc 1000 Sodium thiosulfate g 200 Ammonium chloride g 80 Step 12.Wash for 2 minutes. Step 13.--Form cyan image by treatment for 3 minutes with:

Preparation of high speed silver bleachout taking film (1) Blue sensitive layer containing as a nondiifusing azo yellow color former (2) Gelatin separation layer.

(3) Filter layer of yellow colloidal silver.

(4) Gelatin separation layer.

(5) Green sensitive layer containing as a nondiffusing azo magenta color former:

NHOOC11H35 G N .n our (Synthesis described in FIATFinalReport No,943,1 68) I 7 Step 14.--Wash for 2 minutes.

(6) Gelatin separation layerr 18 .v a (7) Red sensitive layer containing as a nondiffusing cyan component:

EXAMPLE 22 Processing of high speed stlver-bleachout taking 1 film Step 1.Exposure.

Step 2.Development of primary silver image as in Example 20 for 7 minutes.

Step 3.Shortstop and fix as in Example 20 for 5 minutes.

Step 4.--Wash for 5 minutes.

Step 5. --Formation of yellow and magenta dyed layers by coupling for 5 minutes of the color formers in the blue and green sensitive layers with diazotized benzidine-2,2'-disulfonic acid prepared as follows:

1.7 part of benzidine-2,2'-disulfonic acid is dissolved in 300 parts of water containing 5 parts of aqueous sodium hydroxide (10%). A solution of 1 part of sodium nitrite in 10 parts of water is added, and the whole is treated at 10 C. with a solution of 3.5 parts of sulfuric acid (96%) in 25 parts of water. After a period of ten minutes, the resulting diazonium salt solution is buffered to the correct coupling potential with 15 parts of sodium acetate trihydrate.

Step 6.--Wash for 3 minutes.

Step 7 .-I-Iarden for 5 minutes with Water cc 1000 Formaldehyde (36%) cc 25 Sodium bicarbonate g 50 Step 8.Wash for 5 "minutes. Step 9.-Imagewise reduction of color components for 10-20 minutes by treatment with the following bath:

Water cc 1000 Sulfuric acid cc Potassium iodide g 10 Sodium hyposulfite g 5 Quinoline g 50 Step 10.Wash for 5 minutes. Step 11 .Remove residual silver image by treatment for 5 minutes with Water cc 1000 Copper sulfate g 100 Potassium bromide g- 100 Hydrochloric acid cc 5 Step 12.Washfor 5 minutes. Step 13.-Fix residual silver halide by treatment for 5-10 minutes with Water cc 1000 Sodium thiosulfate g 200 Ammonium chloride g 19 Step 15.-Formation of cyan image by treatment for 3 minutes with Water cc 1000 Ferrous ammonium sulfate g 25 Hydrochloric acid (6N) cc 1.5 Hypophosphorous acid (50%) cc- 5 Step 16.-Wash for 15 minutes.

EXAMPLE 23 5,7 dihydroxy 6 nitroso 1,3,4 triazaindolizine having the structure was prepared from 5,7-dihydroxy-1,3,4-triazain dolizine (prepared by the reaction of ethyl malonate and 3-amino-1,2,4-triazole to yield compound (9) of U. S. 2,444,605) by the nitrozation process disclosed in Example 3 of this application.

The nitroso compound, when treated by the solution described in Step 15 of Example 22 yielded a cyan colored image.

EXAMPLE 24 5 amino '7 hydroxy 6 nitroso 1,3,4- triazaindolizines was prepared by nitrosating 5- amino 7 hydroxy 1,3,4 triazaindolizine (prepared by the reaction of ethyl cyanoacetate and 3 amino 1,2,4 triazole to'yield compound of U. S. 2,444,605).

The nitroso compound yielded a cyan image when a photographic emulsion layer was tested by the process indicated as Step of Example 22.

I claim:

1. A photographic silver halide emulsion con taining as a color former a compound capable of reacting with a Water soluble iron salt to form a cyan dye and selected from the class consisting of compounds of the following formulae:

20 in which X is a member selected from the class consisting of =0, =S, =N--Y, or

Y is selected from the class consisting of hydrogen, cyano, aliphatic and aromatic radicals, R and R are selected from the class consisting of hydrogen, alkyl and aryl, and Z is selected from the class consisting of =0 and =NH and the tautomers of said compounds.

2. A photographic emulsion according to claim 1, wherein said color former is 6 amino 2- cyanamin'o 4 hydroxy 5 nitrosopyrimidine.

3. A photographic emulsion according to claim 1, wherein said color former is 2-decylamino-4,6- dihydroxy-5-nitrosopyrimidine.

4. A photographic emulsion according to claim 1, wherein said color former is 2 (2' tetradecoxy 5 sulfophenylamino) 4,6 dihydroxy-5-nitrosopyrimidine.

5. A photographic emulsion according to claim 1, wherein said color former is N (6 amino 4- hydroxy 5 nitroso 2 pyrimidyl) N octadecyltaurine.

6. A photographic emulsion according to claim 1; wherein said color former is N (4,6 dihydroxy 5 nitroso 2 pyrimidyl) N octadecyltaurine.

7. The process which comprises exposing a photographic silver halide emulsion containing as a color former a compound capable of reacting with a water soluble iron salt to form a cyan dye and selected from the class consisting of com pounds of the following formulae:

and

in which X is a member selected from the class consisting of =0, =S, =N-Y, or

Y is selected from the class consisting of hydro" gen, cyano, aliphatic and aromatic radicals, R and R are selected from the class consisting of hydrogen, alkyl and aryl, and Z is selected from the class consisting of =0 and :NH and the tautomers of said compounds, de veloping said emulsion material in a black-andwhite developer, treating with a bleachout solution, and then treating with a water soluble ferrous salt solution to convert the said color former into a positive cyan image.

8. The process of claim 7 wherein said color former is 6 amino 2 cyanamino 4 hydroxy-5-nitrosopyrimidine.

9. The process of claim '7 wherein the color former is 2 decylamino 4,6 dihydroxy 5- nitro'sopyrimidine.

10. The process of claim 7 wherein the color former is 2 (2' tetradecoxy 5 sulfa-phenylamino) 4,6 dihydroxy 5 nitrosopyrimidine.

11. The process of claim 7 wherein the color former is N (6 amino 4 hydroxy 5 nitroso 2 pyrimidyl) N octadecyltaurine.

12. The process of claim 7 wherein the color 10 former is N (4,6 dihydroxy 5 nitroso 2- pyrimidyl) -N-octadecyltaurine.

JOSEPH A. SPRUNG.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date Gaspar Man 3, 1942 Michaelis May 4, 1943 Gaspar Mar. 114, 1944 Peterson July 18,1944 Dersch et a1 Sept. 18, 1945 Chechak Apr. 8, 1947 Taylor May 13, 1947 

1. A PHOTOGRAPHIC SILVER HALIDE EMULSION CONTAINING AS A COLOR FORMER A COMPOUND CAPABLE OF REACTING WITH A WATER SOLUBLE IRON SALT TO FORM A CYAN DYE AND SELECTED FROM THE CLASS CONSISTING OF COMPOUNDS OF THE FOLLOWING FORMULAE: 